JP2022108756A - Conductive film transfer material with carrier film, and method for producing conductive film transfer material with carrier film - Google Patents

Abstract

To provide a conductive film transfer material with a carrier film that is suitable for producing a conductive film having high bending resistance and workability, and a method for producing the same.SOLUTION: A conductive film transfer material 1 with a carrier film includes a carrier film 20, a temporary support 2, a curable resin layer 3 and a conductive layer 4 in this order toward one side in a thickness direction. The temporary support 2 can be peeled off from the curable resin layer 3. The peeling force between the temporary support 2 and the curable resin layer 3 is smaller than the peeling force between the carrier film 20 and the temporary support 2.SELECTED DRAWING: Figure 1

Description

TECHNICAL FIELD The present invention relates to a conductive film transfer material with a carrier film and a method for producing a conductive film transfer material with a carrier film. Specifically, the present invention relates to a conductive film transfer material with a carrier film and a method for manufacturing the conductive film transfer material with a carrier film.

Conductive films comprising a conductive layer of indium tin composite oxide (ITO) are known. The conductive layer is formed into a desired electrode pattern. Conductive films are used, for example, in optical products such as touch panels.

Such a conductive film can be obtained by forming a conductive layer on the surface of a substrate by a sputtering method while conveying the substrate. In such a case, a carrier film is provided on the substrate from the viewpoint of securing mechanical strength and improving transportability.

For example, a transparent conductive film laminate including a carrier film and a transparent conductive film has been proposed (see Patent Document 1, for example). A transparent conductive film includes a transparent substrate, a cured resin layer, and a transparent conductive layer.

Then, when manufacturing a product using the transparent conductive film, the carrier film and the transparent substrate are separated, and the carrier film is removed from the transparent conductive film laminate.

Japanese Patent Application Laid-Open No. 2020-108941

In recent years, flexible displays (foldable, bendable, rollable displays, etc.) require transparent conductive films to have flex resistance.

In Patent Literature 1, the carrier film and the transparent substrate are separated and the carrier film is removed from the transparent conductive film laminate, so the transparent substrate remains on the transparent conductive film. Therefore, the transparent conductive film cannot be made thin, and the bending resistance is lowered.

INDUSTRIAL APPLICABILITY The present invention provides a conductive film transfer material with a carrier film, which is suitable for manufacturing a conductive film excellent in flex resistance and workability, and a method for manufacturing the same.

The present invention [1] includes a carrier film, a temporary support, a cured resin layer, and a conductive layer in order toward one side in the thickness direction, and the temporary support and the cured resin layer are detachable. and a conductive film transfer material with a carrier film, wherein a peeling force between the temporary support and the cured resin layer is smaller than a peeling force between the carrier film and the temporary support.

The present invention [2] includes the conductive film transfer material with a carrier film according to [1] above, wherein a peeling force between the temporary support and the cured resin layer is 1.0 N/24 mm or less. .

The present invention [3] includes the conductive film transfer material with a carrier film according to [1] or [2] above, which has a warpage amount of -10 mm or more and 10 mm or less as measured by the following test.
Test: (1) The conductive film transfer material with the carrier film is cut into squares of 100 mm x 100 mm. (2) The cut conductive film transfer material with carrier film is heated at 140° C. for 90 minutes. (3) Place the cut conductive film transfer material with the carrier film on a horizontal table so that the conductive layer faces upward, measure the vertical height from the horizontal table at each of the four corners, and measure the warp. Quantity. (4) The obtained warp amounts are totaled, the average value is calculated, and the plus warp amount is obtained. (5) When the amount of positive warpage is 0 mm or less, the cut conductive film transfer material with the carrier film is placed on a horizontal table with the carrier film facing upward, and each of the four corners is Measure the vertical height from the horizontal table and use it as the amount of warpage. (6) Add up the obtained warp amounts, calculate the average value, and set it as a minus warp amount.

The present invention [4] is a method for producing a conductive film transfer material with a carrier film according to any one of [1] to [3] above, which comprises a preparation step of preparing a temporary support; A cured resin layer placing step of placing a cured resin layer on one side in the thickness direction of a support, a film forming step of forming a conductive layer on one side of the cured resin layer in the thickness direction, and a thickness of the temporary support. A method for manufacturing a conductive film transfer material with a carrier film, comprising a carrier film placing step of placing the carrier film on the other side of the direction.

The present invention [5] includes the method for producing a conductive film transfer material with a carrier film according to [4] above, wherein a carrier film placement step is performed after the film forming step.

A conductive film transfer material with a carrier film of the present invention includes a carrier film, a temporary support, a cured resin layer, and a conductive layer in order toward one side in the thickness direction. The temporary support and the cured resin layer can be separated. Therefore, a conductive film having excellent bending resistance can be produced.

Specifically, when manufacturing a conductive film, a carrier film is provided from the viewpoint of ensuring mechanical strength and improving transportability. According to this conductive film transfer material with a carrier film, transportability can be improved by providing the carrier film on the other side in the thickness direction of the temporary support during transportation. Moreover, the carrier film can be removed together with the temporary support by separating the temporary support and the cured resin layer after transportation. By doing so, it is possible to obtain a conductive film that does not include a base material (for example, a transparent base material) and that includes a cured resin layer and a conductive layer. And since the obtained conductive film does not have a base material, it is thin and has excellent bending resistance.

Moreover, the peeling force between the temporary support and the cured resin layer is smaller than the peeling force between the carrier film and the temporary support. Therefore, when peeling the temporary support and the cured resin layer, it is possible to suppress peeling between the carrier film and the temporary support. As a result, the carrier film can be removed together with the temporary support by separating the temporary support and the cured resin layer. As a result, workability is excellent.

According to the method for producing a conductive film transfer material with a carrier film of the present invention, the conductive film transfer material with a carrier film of the present invention can be suitably produced.

FIG. 1 shows a cross-sectional view of one embodiment of a conductive film transfer material with a carrier film of the present invention. FIG. 2 shows one embodiment of the method for producing a conductive film transfer material with a carrier film of the present invention. FIG. 2A shows a preparatory step of preparing a temporary support. FIG. 2B shows a cured resin layer placement step of placing a cured resin layer (hard coat layer) on one side in the thickness direction of the temporary support. FIG. 2C shows a film forming step of forming a conductive layer on one side in the thickness direction of the cured resin layer. FIG. 2D shows a carrier film placing step of placing a carrier film on the other side in the thickness direction of the temporary support. FIG. 2E shows a step of peeling off the carrier film from the conductive film transfer material with the carrier film.

One embodiment of the conductive film transfer material with a carrier film of the present invention will be described with reference to FIG.

In FIG. 1, the vertical direction on the page is the vertical direction (thickness direction), the upper side on the page is the upper side (one side in the thickness direction), and the lower side on the page is the lower side (the other side in the thickness direction). Moreover, the left-right direction and the depth direction on the paper surface are plane directions orthogonal to the up-down direction. Specifically, it conforms to the directional arrows in each figure.

<Conductive film transfer material with carrier film>
A conductive film transfer material 1 with a carrier film has a film shape (including a sheet shape) having a predetermined thickness, extends in a plane direction orthogonal to the thickness direction, and has a flat upper surface and a flat lower surface.

Specifically, as shown in FIG. 1, a conductive film transfer material 1 with a carrier film includes a carrier film 20, a temporary support 2, and a conductive film 10 in order toward one side in the thickness direction. More specifically, the conductive film transfer material 1 with a carrier film includes a carrier film 20, a temporary support 2 arranged on the upper surface (one surface in the thickness direction) of the carrier film 20, and an upper surface of the temporary support 2 ( and a conductive film 10 arranged on one side in the thickness direction). Preferably, the carrier film-attached conductive film transfer material 1 includes only the carrier film 20 , the temporary support 2 , and the conductive film 10 .

Further, although the details will be described later, the conductive film 10 does not include a transparent substrate, but includes a cured resin layer 3 and a conductive layer 4 in order toward one side in the thickness direction. Therefore, more specifically, the conductive film transfer material 1 with carrier film includes a carrier film 20, a temporary support 2, a cured resin layer 3, and a conductive layer 4 in order toward one side in the thickness direction.

The thickness of the conductive film transfer material 1 with a carrier film is, for example, 300 μm or less, preferably 150 μm or less, more preferably 100 μm or less.

<Carrier film>
The carrier film 20 is a protective member provided to ensure mechanical strength and improve transportability when manufacturing the conductive film 10 .

The carrier film 20 includes a protective substrate 21 and an adhesive layer 22 in order toward one side in the thickness direction. More specifically, the carrier film 20 includes a protective base material 21 and an adhesive layer 22 arranged on the upper surface (one side in the thickness direction) of the protective base material 21 . Preferably, the carrier film 20 consists of a protective base material 21 and an adhesive layer 22 .

The protective base material 21 is a support base material for ensuring the mechanical strength of the carrier film 20 .

The protective base material 21 has a film shape.

Examples of the protective base material 21 include a polymer film.

Examples of polymer film materials include polyester resins, (meth)acrylic resins, olefin resins, polycarbonate resins, polyethersulfone resins, polyarylate resins, melamine resins, polyamide resins, polyimide resins, cellulose resins, and polystyrene resins. is mentioned. Polyester resins include, for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. (Meth) acrylic resins include, for example, polymethyl methacrylate. Olefin resins include, for example, polyethylene, polypropylene, and cycloolefin polymers. Cellulose resins include, for example, triacetyl cellulose.

The polymer film material preferably includes polyester resin, more preferably polyethylene terephthalate.

The thickness of the protective base material 21 is, for example, 1 μm or more, preferably 5 μm or more, more preferably 10 μm or more, and for example, 200 μm or less, preferably 150 μm or less, more preferably 100 μm or less.

The thickness of the protective base material 21 can be measured using a dial gauge (“DG-205” manufactured by PEACOCK).

The adhesive layer 22 is a layer (pressure-sensitive adhesive layer) for attaching the carrier film 20 (protective base material 21 ) to the temporary support 2 . In addition, it is a layer (easily peelable layer) that can be easily peeled from the temporary support 2 after being attached.

The adhesive layer 22 has a film shape.

The adhesive layer 22 is formed from an adhesive composition.

Examples of adhesive compositions include acrylic adhesive compositions, rubber adhesive compositions, silicone adhesive compositions, polyester adhesive compositions, polyurethane adhesive compositions, and polyamide adhesive compositions. , epoxy-based adhesive compositions, vinyl alkyl ether-based adhesive compositions, and fluorine-based adhesive compositions. These adhesive compositions can be used alone or in combination of two or more.

From the viewpoint of adhesiveness and releasability, the adhesive composition is preferably an acrylic adhesive composition.

The acrylic pressure-sensitive adhesive composition contains, as a polymer component, for example, an acrylic polymer obtained by polymerizing a monomer component containing a (meth)acrylic acid alkyl ester.

(Meth)acrylic acid alkyl esters are acrylic acid alkyl esters and/or methacrylic acid alkyl esters. (Meth)acrylic acid alkyl esters include, for example, linear or branched (meth)acrylic acid alkyl esters having an alkyl moiety having 4 to 14 carbon atoms. Examples of linear or branched (meth)acrylic acid alkyl esters having an alkyl moiety of 4 to 14 carbon atoms include butyl (meth)acrylate, isobutyl (meth)acrylate, and sec (meth)acrylate. -butyl, t-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, (meth)acrylate 2-ethylhexyl acrylate, isooctyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, and tetradecyl (meth)acrylate. The (meth)acrylic acid alkyl esters may be used alone or in combination of two or more. The (meth)acrylic acid alkyl ester preferably includes butyl (meth)acrylate, more preferably butyl acrylate.

The mixing ratio of the (meth)acrylic acid alkyl ester is, for example, 80 parts by mass or more, preferably 85 parts by mass or more, and for example, 99 parts by mass or less, with respect to the total amount of 100 parts by mass of the monomer components. It is 95 parts by mass or less.

The monomer component can contain a functional group-containing monomer in addition to the (meth)acrylic acid alkyl ester.

Functional group-containing monomers include, for example, carboxyl group-containing monomers and hydroxyl group-containing monomers. Carboxyl group-containing monomers include, for example, acrylic acid and methacrylic acid. Hydroxyl group-containing monomers include, for example, 2-hydroxyethyl acrylate and 4-hydroxybutyl acrylate. The functional group-containing monomers can be used singly or in combination of two or more.

The functional group-containing monomer preferably includes a carboxyl group-containing monomer, more preferably acrylic acid.

The blending ratio of the functional group-containing monomer is, for example, 1 part by mass or more, for example 5 parts by mass or more, and 20 parts by mass or less, preferably 15 parts by mass or less with respect to the total amount of 100 parts by mass of the monomer components. .

The acrylic pressure-sensitive adhesive composition can be obtained, for example, by solution polymerization, bulk polymerization, and photopolymerization.

The adhesive composition preferably contains a cross-linking agent. Examples of cross-linking agents include isocyanate-based cross-linking agents, epoxy-based cross-linking agents, melamine-based resins, aziridine derivatives, and metal chelate compounds, preferably epoxy-based cross-linking agents. A crosslinking agent can be used individually or in combination of 2 or more types.

The mixing ratio of the cross-linking agent is, for example, 1 part by mass or more, preferably 4 parts by mass or more, and for example, 15 parts by mass or less, preferably 10 parts by mass or less, relative to 100 parts by mass of the polymer component. be. The release force of the pressure-sensitive adhesive layer 22 can be adjusted by adjusting the mixing ratio of the cross-linking agent.

The adhesive composition may also optionally contain tackifying resins, processing aids, pigments, flame retardants, fillers, softeners, and anti-aging agents.

The thickness of the adhesive layer 22 is, for example, 1 μm or more, preferably 5 μm or more, and for example, 50 μm or less, preferably 30 μm or less.

To prepare the carrier film 20, the pressure-sensitive adhesive layer 22 is arranged on one surface of the protective base material 21 in the thickness direction.

To dispose the adhesive layer 22 on one side in the thickness direction of the protective base material 21, the adhesive composition is applied on one side in the thickness direction of the protective base material 21, heated if necessary, and dried. As a result, the pressure-sensitive adhesive layer 22 is arranged on one surface of the protective base material 21 in the thickness direction.

Moreover, when the pressure-sensitive adhesive composition contains a cross-linking agent, the cross-linking reaction proceeds simultaneously with the above drying or by subsequent aging. Aging conditions are appropriately set according to the type of cross-linking agent. The aging temperature is, for example, 20° C. or higher and, for example, 160° C. or lower. The aging time is, for example, 1 minute or more and, for example, 7 days or less.

Moreover, before or after aging, a release film (not shown) may be laminated on one side in the thickness direction of the pressure-sensitive adhesive layer 22 . Examples of release films include polyethylene terephthalate.

Thus, the carrier film 20 is prepared.

<Temporary support>
The temporary support 2 has a film shape. The temporary support 2 is arranged on the entire lower surface of the conductive film 10 (cured resin layer 3) so as to be in contact with the lower surface of the conductive film 10 (cured resin layer 3).

The temporary support 2 can be peeled off from the cured resin layer 3 .

Although details will be described later, this allows the carrier film 20 to be peeled off together with the temporary support 2 .

More specifically, the peeling force between the temporary support 2 and the cured resin layer 3 is smaller than the peeling force between the carrier film 20 and the temporary support 2 .

Therefore, when the temporary support 2 and the cured resin layer 3 are separated, it is possible to prevent the carrier film 20 from being separated from the temporary support 2 . As a result, the carrier film 20 can be removed together with the temporary support 2 by separating the temporary support 2 and the cured resin layer 3 . As a result, workability is excellent.

On the other hand, if the peeling force between the temporary support 2 and the cured resin layer 3 is greater than the peeling force between the carrier film 20 and the temporary support 2, the temporary support 2 and the cured resin layer 3 are peeled off first. Then, the carrier film 20 and the temporary support 2 are separated. If so, the temporary support 2 cannot be removed together with the carrier film 20 (in other words, the temporary support 2 and the carrier film 20 cannot be peeled off at the same time). As a result, workability is lowered.

Specifically, the peeling force between the temporary support 2 and the cured resin layer 3 is, for example, 1.0 N/24 mm or less, preferably 0.5 N/24 mm or less, and for example, 0.01 N/24 mm or more. be.

Moreover, the peeling force between the carrier film 20 and the temporary support 2 is, for example, 1.5 N/24 mm or less, preferably 1.0 N/24 mm or less, and for example, 0.02 N/24 mm or more.

The difference between the peeling force of the carrier film 20 and the temporary support and the peeling force of the temporary support 2 and the cured resin layer 3 (the peeling force of the carrier film 20 and the temporary support - the peeling of the temporary support 2 and the cured resin layer 3 force) is, for example, 0.01 N/24 mm or more, preferably 0.2 N/24 mm or more, and for example, 1.5 N/24 mm or less, preferably 1.0 N/24 mm or less, more preferably 0.01 N/24 mm or more. It is 5N/24mm or less.

If the peel force is equal to or less than the above upper limit, the temporary support 2 and the cured resin layer 3 can be easily peeled off.

The peel strength can be measured by a peel test described in Examples below.

The temporary support 2 may be, for example, a flexible plastic film. Examples of flexible plastic film materials include olefin resins and polyester resins. Olefin resins include polyethylene, polypropylene, and cycloolefin polymers. Polyester resins include polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate.

The thickness of the temporary support 2 is, for example, 3 μm or more, preferably 10 μm or more, and for example, 200 μm or less, preferably 100 μm or less, more preferably 50 μm or less.

The temporary support 2 is preferably subjected to release treatment in order to adjust the release force within the above range. Examples of the mold release treatment include mold release treatment with a silicone-based, fluorine-based, long-chain alkyl-based, or fatty acid amide-based release agent, or mold release treatment with silica powder.

<Conductive film>
The conductive film 10 includes a cured resin layer 3 and a conductive layer 4 in order toward one side in the thickness direction. More specifically, the conductive film 10 includes a cured resin layer 3 and a conductive layer 4 arranged on the upper surface (one side in the thickness direction) of the cured resin layer 3 . Preferably, the conductive film 10 only includes the cured resin layer 3 and the conductive layer 4 . The conductive film 10 is, for example, a component such as a base material for a touch panel or an electromagnetic wave shield provided in an image display device, that is, it is not an image display device. In other words, the conductive film 10 is a component for producing an image display device or the like, does not include an image display element such as an OLED module, is distributed as a component alone, and is a device that can be used industrially.

<Cured resin layer>
The cured resin layer 3 has a film shape. The cured resin layer 3 is arranged on the entire bottom surface of the conductive layer 4 so as to be in contact with the bottom surface of the conductive layer 4 .

Examples of the cured resin layer 3 include a hard coat layer.

In addition, the following description demonstrates the case where the cured resin layer 3 is a hard-coat layer.

The hard coat layer is a protective layer for preventing the conductive layer 4 from being scratched.

A hard coat layer is formed from a hard coat composition, for example.

The hardcoat composition includes a resin and, optionally, particles. That is, the hard coat layer contains resin and, if necessary, particles.

Examples of resins include thermoplastic resins and curable resins. Examples of thermoplastic resins include polyolefin resins.

Examples of curable resins include active energy ray-curable resins that are cured by irradiation with active energy rays (eg, ultraviolet rays and electron beams) and thermosetting resins that are cured by heating. The curable resin preferably includes an active energy ray curable resin.

Examples of active energy ray-curable resins include (meth)acrylic UV-curable resins, urethane resins, melamine resins, alkyd resins, siloxane-based polymers, and organic silane condensates. As the active energy ray-curable resin, a (meth)acrylic UV-curable resin is preferably used.

Also, the resin can contain a reactive diluent as described, for example, in Japanese Patent Application Laid-Open No. 2008-88309. Specifically, the resin can include a polyfunctional (meth)acrylate.

These resins can be used singly or in combination of two or more.

Examples of particles include metal oxide fine particles and organic fine particles. Materials for metal oxide fine particles include, for example, silica, alumina, titania, zirconia, calcium oxide, tin oxide, indium oxide, cadmium oxide, and antimony oxide. Materials for the organic fine particles include polymethyl methacrylate, silicone, polystyrene, polyurethane, acrylic-styrene copolymer, benzoguanamine, melamine, and polycarbonate.

The particles can be used singly or in combination of two or more.

By adjusting the mixture ratio of the particles and/or the average particle diameter of the particles to a predetermined ratio, the arithmetic mean roughness Ra of the conductive layer 4, which will be described later, can be adjusted within a predetermined range, which will be described later.

Specifically, the mixing ratio of the particles is, for example, 1 part by mass or more, preferably 3 parts by mass or more, or, for example, 10 parts by mass or more, or, for example, 20 parts by mass, with respect to 100 parts by mass of the resin. It is below.

If the mixing ratio of the particles is equal to or less than the above upper limit, the arithmetic mean roughness Ra of the conductive layer 4, which will be described later, can be adjusted within a predetermined range, which will be described later.

The average particle size of the particles is, for example, 10 μm or less, preferably 8 μm or less, or, for example, 1 nm or more. When nanoparticles are used as the particles, the average particle size of the particles is, for example, 100 nm or less, preferably 70 nm or less, or, for example, 1 nm or more. The average particle size of the particles is determined, for example, as a D50 value (cumulative 50% median diameter) based on the particle size distribution determined by the particle size distribution measurement method in the laser scattering method.

If the average particle size of the particles is within the above range, the arithmetic mean roughness Ra of the conductive layer 4, which will be described later, can be adjusted within a predetermined range, which will be described later.

In addition, the hard coat composition may optionally contain a thixotropy-imparting agent, a photopolymerization initiator, a filler (eg, organic clay), and a leveling agent in appropriate proportions. Also, the hard coat composition can be diluted with a known solvent.

To form the hard coat layer, a diluted hard coat composition is applied to one surface of the temporary support 2 in the thickness direction, and if necessary, heated to dry, although the details will be described later. After drying, the hard coat composition is cured by, for example, active energy ray irradiation.

This forms a hard coat layer.

The thickness of the hard coat layer is, for example, 1 μm or more and 7 μm or less, preferably 3 μm or less, more preferably 2.5 μm or less, still more preferably 1.5 μm or less.

Moreover, the thickness of the hard coat layer can be measured by cross-sectional observation using, for example, a transmission electron microscope.

<Conductive layer>
Conductive layer 4 is amorphous or crystalline. Moreover, the conductive layer 4 is preferably a transparent layer (transparent conductive layer) exhibiting excellent conductivity.

The conductive layer 4 has a film shape. The conductive layer 4 is arranged over the entire upper surface of the cured resin layer 3 so as to be in contact with the upper surface of the cured resin layer 3 .

Examples of materials for the conductive layer 4 include metal oxides. The metal oxide contains, for example, at least one metal element selected from the group consisting of In, Sn, Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd and W. include. The metal oxide may be further doped with a metal element shown in the above group, if necessary.

Examples of conductive layer 4 include indium-containing oxides and antimony-containing oxides. Indium-containing oxides include, for example, indium-tin composite oxide (ITO). Antimony-containing oxides include, for example, antimony-tin composite oxide (ATO). From the viewpoint of low resistance, the conductive layer 4 is preferably an indium-containing oxide, more preferably ITO.

When ITO is used as the material of the conductive layer ₄ , the tin oxide ₍ SnO ₂ ) content is, for example, 0.5% by mass or more, preferably , 3% by mass or more, more preferably 5% by mass or more, and for example, 15% by mass or less, preferably 13% by mass or less. If the content of tin oxide is at least the above lower limit, the durability of the ITO layer can be further improved. When the content of tin oxide is equal to or less than the above upper limit, the crystal conversion of the ITO layer can be facilitated, and the stability of transparency and specific resistance can be improved.

"ITO" in this specification may be a composite oxide containing at least indium (In) and tin (Sn), and may contain additional components other than these. Examples of additional components include metal elements other than In and Sn. Specific examples of such metal elements include Zn, Ga, Sb, Ti, Si, Zr, Mg, Al, Au, Ag, Cu, Pd, W, Fe, Pb, Ni, Nb, Cr and Ga. mentioned.

Conductive layer 4 is preferably crystalline.

If the conductive layer 4 is crystalline, the surface resistivity, which will be described later, can be lowered.

The crystallinity of the conductive layer 4 is determined, for example, by immersing the conductive film 10 in hydrochloric acid (20° C., concentration 5% by mass) for 15 minutes, followed by washing with water and drying. It can be judged by measuring the resistance between terminals for about 15 mm. In the conductive film 10 after immersion, washing with water and drying, the conductive layer 4 is crystalline when the resistance between the terminals over 15 mm is 10 kΩ or less. On the other hand, if the resistance exceeds 10 kΩ, the conductive layer 4 is amorphous.

The specific resistance of the upper surface of the conductive layer 4 is, for example, 20×10 ⁻⁴ Ω·cm or less, preferably 8.0×10 ⁻⁴ Ω·cm or less, or for example, 0.1×10 ⁻⁴ Ω·cm. cm or more. A specific resistance can be measured by a four-probe method in accordance with JIS K7194 (1994).

The surface resistivity of the upper surface of the conductive layer 4 is, for example, 150Ω/square or less, preferably 50Ω/square or less, or, for example, 0.1Ω/square or more. Surface resistivity can be measured by a four-probe method in accordance with JIS K7194 (1994).

If the surface resistivity is equal to or less than the above upper limit, the conductive film 10 can be used for, for example, a large touch panel.

The arithmetic mean roughness Ra of the conductive layer 4 (specifically, the arithmetic mean roughness Ra of one side in the thickness direction of the conductive layer 4) is, for example, 7.0 nm or less, preferably 1.5 nm or less, or, for example, 0 .2 nm or more.

The conductive layer 4 can be obtained from an observation image of 1 μm square by an AFM (atomic force microscope), for example, in accordance with JIS B0681-6 (2017).

The thickness of the conductive layer 4 is, for example, 10 nm or more, preferably 30 nm or more, and for example, 150 nm or less, preferably 100 nm or less, more preferably 70 nm or less. The thickness of the conductive layer 4 can be measured, for example, by observing the cross section of the conductive film 10 using a transmission electron microscope.

The total light transmittance (JIS K 7375-2008) of the conductive layer 4 is, for example, 50% or more, preferably 60% or more.

<Method for producing conductive film transfer material with carrier film>
A method for manufacturing a conductive film transfer material 1 with a carrier film includes a preparation step of preparing a temporary support 2 and a cured resin layer 3 (hard coat layer) disposed on one side of the temporary support 2 in the thickness direction. A layer arrangement step, a film formation step of forming a conductive layer 4 on one side of the cured resin layer 3 in the thickness direction, and a carrier film arrangement step of arranging a carrier film 20 on the other side of the temporary support 2 in the thickness direction. Prepare.

Moreover, in this manufacturing method, preferably, the carrier film disposing step is performed after the film forming step.

If the carrier film placing step is performed after the film forming step, the carrier film 20 is not placed during the film forming step. can be suppressed.

In the preparation step, as shown in FIG. 2A, the temporary support 2 is prepared.

In the cured resin layer placement step, a cured resin layer 3 (hard coat layer) is placed on one side of the temporary support 2 in the thickness direction, as shown in FIG. 2B.

In order to arrange the cured resin layer 3 (hard coat layer) on one side in the thickness direction of the temporary support 2, first, the surface of the temporary support 2 (the surface subjected to the above-described release treatment, or the above-described The surface that has not been subjected to mold release treatment) is subjected to surface treatment.

Surface treatments include, for example, corona treatment, plasma treatment, flame treatment, ozone treatment, primer treatment, glow treatment, and saponification treatment. The surface treatment preferably includes plasma treatment.

Next, a dilute solution of the hard coat composition is applied to one surface of the temporary support 2 in the thickness direction, and after drying, the hard coat composition is cured by ultraviolet irradiation or heating. As a result, a cured resin layer 3 (hard coat layer) is formed on one surface of the temporary support 2 in the thickness direction. As a result, the conveying sheet 30 having the temporary support 2 and the cured resin layer 3 in order toward one side in the thickness direction is obtained.

In the film forming step, as shown in FIG. 2C, the conductive layer 4 is formed on one surface of the cured resin layer 3 in the thickness direction.

In order to form the conductive layer 4 on one side of the cured resin layer 3 in the thickness direction, first, the conveying sheet 30 is wound around a delivery roll (not shown).

Next, the conveying sheet 30 is delivered from the delivery roll. Then, while conveying the conveying sheet 30 downstream in the conveying direction, the conductive layer 4 is formed on one surface of the cured resin layer 3 in the thickness direction by a sputtering method.

The conveying speed is, for example, 1 m/min or more, preferably 2 m/min or more, and for example, 10 m/min or less, preferably 7 m/min or less.

In the sputtering method, a target (material of the conductive layer 4) and the cured resin layer 3 are placed facing each other in a vacuum chamber. Next, gas is supplied and voltage is applied from the power supply. This causes the gas ions to accelerate and irradiate the target, ejecting the target material from the target surface. Then, the target material is deposited on one surface of the cured resin layer 3 in the thickness direction.

Gases include, for example, inert gases. Examples of inert gases include argon gas. Also, if necessary, for example, a reactive gas (eg, oxygen gas) can be used together. When a reactive gas is used together, the flow ratio (sccm) of the reactive gas is not particularly limited. Specifically, the flow rate ratio of the reactive gas is, for example, 0.1 flow % or more and 100 flow % or less with respect to the total flow rate ratio of the sputtering gas and the reactive gas.

The atmospheric pressure during sputtering is, for example, 0.1 Pa or more, or, for example, 1.0 Pa or less, preferably 0.7 Pa or less.

The power supply can be, for example, a DC power supply, an AC power supply, an MF power supply, and an RF power supply. A combination of these may also be used.

The discharge output is, for example, 10 kW or more, preferably 20 kW or more, and, for example, 305 kW or less.

Thus, the conductive layer 4 is arranged on one surface of the cured resin layer 3 in the thickness direction.

In the carrier film placement step, a carrier film 20 is placed on the other side of the temporary support 2 in the thickness direction, as shown in FIG. 2D. In order to dispose the carrier film 20 on the other side of the temporary support 2 in the thickness direction, first, the carrier film 20 is prepared by the method described above.

Next, the carrier film 20 is placed on the other thickness direction side of the temporary support 2 with the adhesive layer 22 of the carrier film 20 interposed therebetween.

After that, from the viewpoint of improving the crystallinity, the conductive layer 4 formed can be heated. The heating temperature is, for example, 80° C. or higher and 160° C. or lower. Also, the heating time is, for example, 10 minutes or more and, for example, 120 minutes or less.

As described above, the conductive film transfer material 1 with a carrier film is obtained, which includes the carrier film 20, the temporary support 2, the cured resin layer 3, and the conductive layer 4 in order toward one side in the thickness direction.

The amount of warpage of the carrier film-attached conductive film transfer material 1 measured by the following test is, for example, -10 mm or more, preferably -5 mm or more, more preferably -3 mm or more, and for example, 10 mm or less. is 5 mm or less, more preferably 3 mm or less, still more preferably 2 mm or less.

In the test, first, the conductive film transfer material 1 with carrier film is cut into a square of 100 mm×100 mm. The cut conductive film transfer material 1 with carrier film is heated at 140° C. for 90 minutes. Next, the cut conductive film transfer material 1 with the carrier film is placed on a horizontal table so that the conductive layer 4 is on the upper side, and the vertical height from the horizontal table is measured at each of the four corners, and the warp is measured. Quantity. The warp amounts thus obtained are totaled, the average value is calculated, and the plus warp amount is obtained. When the amount of positive warp is 0 mm or less, the cut conductive film transfer material 1 with carrier film is placed on a horizontal table with the carrier film 20 facing upward, and at each of the four corners, Measure the vertical height from the horizontal table and use it as the amount of warpage. The obtained warp amounts are totaled, the average value is calculated, and the negative warp amount is obtained.

If the amount of warpage is within the above range, the transportability is excellent.

Then, when manufacturing a product using the conductive film 10, the carrier film 20 is peeled off from the conductive film transfer material 1 with the carrier film, as shown in FIG. 2E. Specifically, the temporary support 2 and the cured resin layer 3 are separated, and the carrier film 20 is separated together with the temporary support 2 .

Thereby, the conductive film 10 having the cured resin layer 3 and the conductive layer 4 in order toward one side in the thickness direction is obtained.

Also, the conductive layer 4 can be patterned before or after the carrier film 20 is peeled off. Patterning is performed, for example, by etching.

<Effect>
A conductive film transfer material 1 with a carrier film includes a carrier film 20, a temporary support 2, a cured resin layer 3 (hard coat layer), and a conductive layer 4 in order toward one side in the thickness direction. The temporary support 2 and the cured resin layer 3 (hard coat layer) can be separated. Therefore, the conductive film 10 having excellent bending resistance can be manufactured.

Specifically, when manufacturing the conductive film 10, a carrier film 20 is provided from the viewpoint of ensuring mechanical strength and improving transportability. According to this conductive film transfer material 1 with a carrier film, by providing the carrier film 20 on the other side of the temporary support 2 in the thickness direction, the transportability can be improved. Further, the carrier film 20 can be removed together with the temporary support 2 by peeling the temporary support 2 and the cured resin layer 3 after transportation. As a result, the conductive film 10 having the cured resin layer 3 and the conductive layer 4 without a base material (for example, a transparent base material) can be obtained. And since the obtained conductive film 10 does not have a base material, it is thin and has excellent bending resistance.

Moreover, the peeling force between the temporary support 2 and the cured resin layer 3 is smaller than the peeling force between the carrier film 20 and the temporary support 2 . Therefore, when the temporary support 2 and the cured resin layer 3 are separated, it is possible to prevent the carrier film 20 from being separated from the temporary support 2 . As a result, the carrier film 20 can be removed together with the temporary support 2 by separating the temporary support 2 and the cured resin layer 3 . As a result, workability is excellent.

According to the method for manufacturing the conductive film transfer material 20 with the carrier film, the conductive film transfer material 1 with the carrier film can be manufactured favorably.

<Modification>
In the modified example, the same reference numerals are given to the same members and steps as in the embodiment, and detailed description thereof will be omitted. In addition, the modified example can have the same effects as the one embodiment, unless otherwise specified. Furthermore, one embodiment and its modifications can be combined as appropriate.

In the above description, the cured resin layer 3 is a hard coat layer, but the cured resin layer 3 may be an optical adjustment layer.

The optical adjustment layer suppresses the visibility of the pattern of the conductive layer 4 and suppresses reflection at the interface in the conductive film 10, while ensuring excellent transparency of the conductive film 10. It is a layer that adjusts the optical properties (for example, refractive index) of

Moreover, as the cured resin layer 3, a hard coat layer and an optical adjustment layer can be used together (multilayer including a hard coat layer and an optical adjustment layer).

EXAMPLES Examples and comparative examples are shown below to describe the present invention more specifically. In addition, the present invention is not limited to Examples and Comparative Examples. In addition, specific numerical values such as the mixing ratio (content ratio), physical property values, and parameters used in the following description are the corresponding mixing ratios ( Content ratio), physical properties, parameters, etc. be able to.

1. Production of conductive film transfer material with carrier film Example 1
<Preparation process>
As a temporary support, a polyethylene terephthalate base material (manufactured by Panac Co., Ltd., trade name "Pana-Peel" TP series) having one side subjected to mold release treatment was prepared.

<Curing resin layer placement step>
A hard coat composition containing 100 parts by mass of an ultraviolet curable resin composition (manufactured by DIC under the trade name “Luxidia (registered trademark) V-6000”) and 3 parts by mass of a photoreaction initiator was prepared.

Then, the hard coat composition was applied to the release-treated surface of the temporary support using a gravure coater so that the thickness after drying was 1 μm. After that, the coating film was heated at 80°C. Then, the hard coat composition was cured by irradiating ultraviolet light with an accumulated light amount of 250 mJ/cm ² from a high-pressure mercury lamp. As a result, a hard coat layer was formed on one surface of the temporary support in the thickness direction to obtain a conveying sheet.

<Film formation process>
A sintered body target containing indium oxide and tin oxide at a mass ratio of 90:10 is attached to a parallel plate winding type magnetron sputtering apparatus, and the partial pressure of water is reduced by evacuation while conveying the conveying sheet. was evacuated to 5×10 ⁻⁴ Pa. After that, while adjusting the introduction amounts of argon gas and oxygen gas, while conveying the conveying sheet at a conveying speed of 4.0 m/min and a conveying tension of 200 to 500 N, an output of 24.0 m was applied to one surface in the thickness direction of the hard coat layer. The film was deposited by DC sputtering at 2 kW. As a result, a conductive layer (ITO layer) having a thickness of 50 nm was formed on one surface of the hard coat layer in the thickness direction.

<Carrier film arrangement process>
A PET film having a thickness of 125 μm was prepared as a protective base material.

Then, an adhesive composition was prepared. Specifically, an acrylic polymer was obtained by solution polymerization of a monomer component containing butyl acrylate/acrylic acid (100/6). An adhesive composition was prepared by adding 6 parts by weight of an epoxy-based cross-linking agent to 100 parts by weight of this acrylic polymer.

Next, this pressure-sensitive adhesive composition was applied to one surface in the thickness direction of a PET film (protective substrate) and heated at 150° C. for 90 seconds to form a pressure-sensitive adhesive layer having a thickness of 10 μm. Next, a silicone-treated surface of a PET film (release liner) having a thickness of 25 μm was adhered to one surface in the thickness direction of the pressure-sensitive adhesive layer and stored at 50° C. for 2 days. A carrier film was thus obtained.

After that, the PET film (release liner) was peeled off, and one side in the thickness direction of the pressure-sensitive adhesive layer and the other side in the thickness direction of the temporary support were bonded together. As a result, a conductive film with a carrier film was obtained, which includes a carrier film, a temporary support, a hard coat layer, and a conductive layer in order toward one side in the thickness direction.

Example 2 and Example 3
A conductive film with a carrier film was obtained in the same manner as in Example 1. However, the thickness of the hard coat layer was changed according to Table 1.

Example 4
A conductive film transfer material with a carrier film was obtained in the same manner as in Example 1. However, after the carrier film placement step, heat treatment was performed at 140° C. for 90 minutes in a heat open to convert the conductive layer into crystals.

Example 5
A conductive film transfer material with a carrier film was obtained in the same manner as in Example 1. However, in the step of arranging the cured resin layer, the ultraviolet curable resin composition (manufactured by DIC under the trade name “Unidic ELS888”) and the ultraviolet curable resin composition (manufactured by DIC under the trade name “Unidic RS28-605”) are combined. Hardcoat compositions mixed in a weight ratio of 8:2 were used.

Example 6
A conductive film transfer material with a carrier film was obtained in the same manner as in Example 1. However, in the step of arranging the cured resin layer, the ultraviolet curable resin composition (manufactured by DIC under the trade name “Unidic ELS888”) and the ultraviolet curable resin composition (manufactured by DIC under the trade name “Unidic RS28-605”) are combined. A hardcoat composition mixed in a weight ratio of 2:8 was used. Also, the thickness of the hard coat layer was changed according to Table 1.

Comparative Example 1 and Comparative Example 2
A conductive film with a carrier film was obtained in the same manner as in Example 1. However, the thickness of the hard coat layer was changed according to Table 1. Further, after the carrier film disposing step, a heat treatment was performed at 140° C. for 90 minutes in a heat open to convert the conductive layer into crystals.

Comparative example 3
The preparation process, the cured resin layer placement process, and the film formation process were performed in the same manner as in Example 1. In other words, in Comparative Example 3, the carrier film placement step was not performed. As a result, a laminate having a temporary support, a hard coat layer, and a conductive layer 4 in this order toward one side in the thickness direction was obtained.

2. Evaluation (peeling force)
The peel strength (the peel strength between the temporary support and the cured resin layer, and the peel strength between the carrier film and the temporary support) is determined by a peel test ( It was measured by a flat plate cross-stage method). Table 1 shows the results. Hereinafter, a method for measuring the peel force between the temporary support and the cured resin layer and a method for measuring the peel force between the carrier film and the temporary support will be specifically described in detail.

First, the method for measuring the peeling force between the temporary support and the cured resin layer will be described in detail. First, in each example and each comparative example, a preparation step, a cured resin layer placement step, and a film formation step are performed in order to form a temporary support, a temporary support, a cured resin layer, and a conductive layer. A first peel force test sample was prepared in order toward one side in the thickness direction.

The peel strength between the temporary support and the cured resin layer was measured according to the following steps for the first peel strength test sample. In Examples 1 to 3, 5 and 6, Steps B to F below were performed, and in Example 4 and Comparative Examples 1 and 2, Steps A to F below were performed.
Step A: The first peel strength test sample was heated in a hot air oven at 140°C for 90 minutes.
Step B: A sample for the first peel force test was cut to 24 mm x 100 mm.
Step C: A glass substrate was attached to one surface of the conductive layer of the first peel force test sample in the thickness direction via an adhesive layer having a peel force of 5 N/24 mm or more. A roller was used for lamination.
Step D: A 24 mm x 100 mm portion of an adhesive tape (Sekisui Cellotape No. 252) of 24 mm x 150 mm was adhered to the other side in the thickness direction of the temporary support of the conductive film transfer material. That is, of the 24 mm×150 mm adhesive tape, 24 mm×100 mm is the bonded portion and 24 mm×50 mm unbonded portion. A roller was used for lamination.
Step E: The sample prepared in step D was set on the stage, and the non-bonded portion of the adhesive tape (Sekisui Cellotape No. 252) was bonded to the measurement probe.
Step F: Calculate the average value of the peel force (peeling speed: 0.1 m/min, peel angle: 90°) between moving from 20 mm to 80 mm with the peel distance of the unbonded portion and the bonded portion being 0 mm. did.

Next, a method for measuring the peel strength between the carrier film and the temporary support will be described in detail. First, in each example and each comparative example, the adhesive surface of the carrier film was subjected to a release treatment of a polyethylene terephthalate base material (manufactured by Panac Co., Ltd., trade name "Pana-Peel" TP series), which was subjected to a release treatment on one side. The untreated surfaces were pasted together. A roller was used for lamination. In this way, a sample for a second peel strength test, which includes the carrier film and the temporary support, was prepared.

The peel force between the carrier film and the temporary support was measured according to the following steps for the second peel force test sample. In Examples 1 to 3, 5 and 6 and Comparative Example 1, Steps H to M below were performed, and in Example 4 and Comparative Example 2, Steps G to M below were performed.
Step G: The second peel test sample was heated in a hot air oven at 140°C for 90 minutes.
Step H: A sample for the second peel strength test was cut to 24 mm x 100 mm.
Step I: A glass substrate was attached to the temporary support surface of the sample for the second peel force test via an adhesive layer having a peel force of 5 N/24 mm or more. A roller was used for lamination.
Step J: A 24 mm x 100 mm portion of a 24 mm x 150 mm adhesive tape (Sekisui Cello Tape No. 252) was adhered to the carrier film surface of the second peel force test sample. That is, of the 24 mm×150 mm adhesive tape, 24 mm×100 mm is the bonded portion and 24 mm×50 mm unbonded portion. A roller was used for lamination.
Step K: The sample prepared in step D was set on the stage, and the non-bonded portion of the adhesive tape (Sekisui Cellotape No. 252) was bonded to the measurement probe.
Step M: Calculate the average value of the peel force between moving from 20 mm to 80 mm with the unbonded part and the bonded part having a peel distance of 0 mm (peeling speed: 0.1 m / min, peeling angle: 90 °). did.

(Peelability)
The peelability was evaluated according to the following criteria. Table 1 shows the results.
Criteria ◯: In the evaluation of the peel strength described above, the peel strength between the temporary support and the cured resin layer is smaller than the peel strength between the carrier film and the temporary support.
x: In the above peel strength evaluation, the peel strength between the temporary support and the cured resin layer is greater than the peel strength between the carrier film and the temporary support.

(Amount of warpage)
The conductive film transfer material with the carrier film of each example and each comparative example was cut into squares of 100 mm×100 mm. The cut conductive film transfer material with carrier film was heated at 140° C. for 90 minutes. Next, the cut conductive film transfer material with carrier film is placed on a horizontal table so that the conductive layer 4 faces upward, and the vertical height from the horizontal table is measured at each of the four corners, and the amount of warpage and The obtained warp amounts were totaled, and the average value was calculated as a positive warp amount. When the positive warp amount is 0 mm or less, the cut conductive film transfer material with carrier film is placed on a horizontal table so that the carrier film faces upward, and at each of the four corners, the horizontal table The vertical height from the center was measured and used as the amount of warpage. The obtained warp amounts were totaled, and the average value was calculated as a negative warp amount. Table 1 shows the results.

3. Discussion Examples 1 to 6, in which the peeling force between the temporary support and the cured resin layer is smaller than the peeling force between the carrier film and the temporary support, are excellent in peelability. That is, in Examples 1 to 6, since the temporary support and the cured resin layer are separated before the carrier film and the temporary support are separated, the carrier film can be removed together with the temporary support. can. As a result, it turns out that workability|operativity is excellent. By the peeling described above, a conductive film having a cured resin layer and a conductive layer without a substrate (for example, a transparent substrate) can be obtained. Since the obtained conductive film does not have a substrate, it is thin and has excellent bending resistance.

On the other hand, in Comparative Examples 1 and 2 in which the peeling force between the temporary support and the cured resin layer is greater than the peeling force between the carrier film and the temporary support, the peelability is lowered. That is, in Comparative Examples 1 and 2, the carrier film and the temporary support are separated before the temporary support and the cured resin layer are separated. Then, the temporary support cannot be removed together with the carrier film (the temporary support and the carrier film cannot be peeled off at the same time). As a result, workability is lowered.

REFERENCE SIGNS LIST 1 conductive film transfer material with carrier film 2 temporary support 3 cured resin layer 4 conductive layer 10 conductive film 20 carrier film

Claims (5)

A carrier film, a temporary support, a cured resin layer, and a conductive layer are provided in order toward one side in the thickness direction,
The temporary support and the cured resin layer are detachable,
A conductive film transfer material with a carrier film, wherein a peeling force between the temporary support and the cured resin layer is smaller than a peeling force between the carrier film and the temporary support. 2. The conductive film transfer material with a carrier film according to claim 1, wherein a peeling force between said temporary support and said cured resin layer is 1.0 N/24 mm or less. 3. The conductive film transfer material with a carrier film according to claim 1, wherein the amount of warp measured by the following test is -10 mm or more and 10 mm or less.
Test: (1) The conductive film transfer material with the carrier film is cut into squares of 100 mm x 100 mm.
(2) The cut conductive film transfer material with carrier film is heated at 140° C. for 90 minutes.
(3) Place the cut conductive film transfer material with the carrier film on a horizontal table so that the conductive layer faces upward, measure the vertical height from the horizontal table at each of the four corners, and measure the warp. Quantity.
(4) The obtained warp amounts are totaled, the average value is calculated, and the plus warp amount is obtained.
(5) When the amount of positive warpage is 0 mm or less, the cut conductive film transfer material with the carrier film is placed on a horizontal table with the carrier film facing upward, and each of the four corners is Measure the vertical height from the horizontal table and use it as the amount of warpage.
(6) Add up the obtained warp amounts, calculate the average value, and set it as a minus warp amount. A method for producing a conductive film transfer material with a carrier film according to any one of claims 1 to 3,
A preparation step of preparing a temporary support;
A cured resin layer arranging step of arranging a cured resin layer on one side in the thickness direction of the temporary support;
A film forming step of forming a conductive layer on one side in the thickness direction of the cured resin layer;
A method for producing a conductive film transfer material with a carrier film, comprising a carrier film placing step of placing a carrier film on the other side in the thickness direction of the temporary support. 5. The method for manufacturing a conductive film transfer material with a carrier film according to claim 4, wherein a carrier film disposing step is performed after the film forming step.

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